Mixtures of phenolic and inorganic materials with antimicrobial activity

ABSTRACT

Plastic films, fibers and articles are provided long-term antimicrobial activity with a combination of certain phenolic and inorganic antimicrobial agents. The plastic films, fibers and articles with antimicrobial activity exhibit superior resistance to discoloration, may be processed at high temperature, and maintain physical properties upon weathering, especially upon exposure to ultraviolet radiation.

[0001] This application claims the benefit under 35 USC 119(e) of U.S.Provisional Application Serial No. 60/234,433, filed Sep. 21, 2000.

[0002] The present invention relates to combinations of phenolic andinorganic compounds which exhibit excellent antimicrobial activity whenincorporated into a substrate resin, which mixtures do not exhibit thenegative effects associated with the use of either alone. Plasticarticles manufactured via a variety of processes from such resins areprovided long term antimicrobial activity and exhibit superiorresistance to discoloration and maintenance of physical properties,especially upon exposure to ultraviolet radiation.

[0003] Triclosan, or Irgaguard®, Ciba Specialty Chemicals,2,4,4′-trichloro-2′-hydroxydiphenyl ether, is a known antimicrobial forplastics applications. It is known to have high activity againstnumerous gram-positive and gram-negative bacterial. It can beincorporated as a neat material or via a masterbatch into a variety ofpolymer substrates, for example, polyethylenes such as LDPE, HDPE, MDPE,polypropylene (PP), acrylonitrile-butadiene-styrene terpolymer (ABS),styrene-acrylonitrile copolymer (SAN), polystyrene (PS), polyacrylates,polymethyl methacrylate (PMMA), polyamide, polyesters, polyvinylchloride (PVC), polymer latex, polyurethane (PUR), thermoplasticpolyurethane (TPU), unsaturated polyester (UP), urea formaldehyde resin(UF), etc. Irgaguard® exhibits high activity at the surface of plasticarticles and the activity remains after repeated washing of plasticarticles. Further, Irgaguard® has a good toxicological profile.

[0004] Disadvantages of Irgaguard® are that plastic articles formulatedwith it exhibit strong discloloration upon weathering. For example,polypropylene samples containing Irgaguard® exposed in a Xenon ArcWeather-Ometer at 035 W/m², 63° C. discolor within hours. Further,processing at temperatures greater than 250° C. is poblematic due to thevolatility of Irgaguard®.

[0005] Silver based materials, such as colloidal silver, silver nitrate,silver sulfate, silver chloride, silver complexes and silver ioncontaining zeolites are known antimicrobial agents for plastic articles.Silver compounds exhibit high activity against microorganisms and theyhave a good toxicological profile. High processing temperatures arepossible with silver compounds (greater than 300° C.).

[0006] Disadvantages of silver based antimicrobials are that plasticarticles containing them often exhibit discloloration upon weathering,and the activity on the surface of the articles is often lost afterrepeated washing.

[0007] It has been found, surprisingly, that a combination of certainphenolic compounds with certain inorganic compounds avoids thedisadvantages of using either Irgaguard® or silver based antimicrobialsalone in plastic articles while providing excellent long-termantimicrobial activity to the articles.

OBJECTS OF THE INVENTION

[0008] An object of the present invention is to provide a novel mixtureof antimicrobial agents for plastics applications.

[0009] Another object of the invention is to provide plastic articles orfilms with antimicrobial activity which also exhibit superior resistanceto discoloration, may be processed at high temperatures, and whichmaintain physical properties upon weathering, especially upon exposureto UV radiation.

DETAILED DESCRIPTION

[0010] The instant invention pertains to a novel mixture ofantimicrobial agents for plastics applications which comprises

[0011] a) at least one phenolic antimicrobial compound, and

[0012] b) at least one inorganic antimicrobial compound,

[0013] wherein

[0014] the phenolic antimicrobial compound is of the formula (I)

[0015] wherein

[0016] n is 0 or 1,

[0017] R₁ and R₂ are hydrogen or chlorine,

[0018] R₃ is hydrogen or hydroxyl,

[0019] R₄, R₅ and R₆ are hydrogen or chlorine,

[0020] R₇ is hydroxyl, and

[0021] X is —O— or —CH₂—,

[0022] and wherein the inorganic antimicrobial compound is selected fromthe group consisting of zinc oxide, copper and copper compounds,colloidal silver, silver nitrate, silver sulphate, silver chloride,silver complexes, metal-containing zeolites and surface-modifiedmetal-containing zeolites,

[0023] and wherein the ratio of components a):b) is from about 1:9 toabout 9:1.

[0024] Preferred phenolic antimicrobial compounds of component a) areo-benzyl-phenol, 2-benzyl-4-chloro-phenol,2,4,4′-trichloro-2′-hydroxydiphenyl ether,4,4′-dichloro-2-hydroxydiphenyl ether,5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol,2,2′-methylenbis-(4-chloro-phenol) and 2,4,6-trichlorophenol.

[0025] Most preferred phenolic antimicrobial compounds of component a)are 2,4,4′-trichloro-2′-hydroxydiphenyl ether and4,4′-dichloro-2-hydroxydiphenyl ether.

[0026] The metal-containing zeolites of component b) are those such asdescribed in U.S. Pat. Nos. 4,775,585, 4,911,898, 4,911,899 and6,071,542, the disclosures of which are hereby incorporated byreference. A zeolite is generally aluminosilicate having a threedimensionally grown skeleton structure and is generally represented byxM_(2/n)O.Al₂O₃.ySiO₂.zH₂O, written with Al₂O₃ as a basis, wherein Mrepresents an ion-exchangeable metal ion, which is usually the ion of amonovalent or divalent metal; n corresponds to the valence of the metal;x is a coefficient of the metal oxide; y is a coefficient of silica; andz is the number of water of crystallization. The zeolites of the presentinvention have a specific surface area of at least 150 m²/g.

[0027] Antibacterial metals for use in metal-containing zeolites includesilver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium,cobalt, nickel, zirconium, or a combination of two or more of thesemetals. Preference is given to silver, copper, zinc and zirconium, or acombination of these. Especially preferred metals are silver alone or acombination of silver with copper, zinc or zirconium.

[0028] Particularly preferred inorganic antimicrobial compounds ofcomponent b) are surface-modified metal-containing zeolites according toU.S. Pat. No. 6,071,542.

[0029] Especially preferred is the antimicrobial mixture whereincomponent a) is 2,4,4′-trichloro-2′-hydroxydiphenyl ether and whereinthe inorganic antimicrobial compound of component b) is asurface-modified silver-containing zeolite. The term “silver-containing”includes the combination of silver with other metals such as zinc,copper and zirconium. BACTEKILLER BM-102GA (Kanebo) is an example of asurface-modified silver-containing zeolite according to U.S. Pat. No.6,071,542.

[0030] In addition to zeolites, it is also contemplated thatantibacterial metals such as silver, silver compounds and silvercomplexes may be supported on other inert materials, for example SiO₂,TiO₂ and glass.

[0031] The instant invention also pertains to plastic films, fibers orarticles that comprise the novel mixture of components a) and b).

[0032] The novel antimicrobial mixture of components a) and b) may beincorporated into the plastic resin prior to its being subjected to suchmanufacturing processes as blown film, rotational molding fiberspinning, etc. The mixture of components a) and b) is able to withstanddemanding processing conditions such as high temperature, e.g.temperatures greater than 200° C.

[0033] The plastic films, fibers and articles comprising the presentantimicrobial mixture of components a) and b) is suitable for outdoorexposure; they are resistant to weathering and UV light degradation.

[0034] The antimicrobial mixture of components a) and b) exhibit goodlong-term activity and a good toxicological profile.

[0035] Triclosan containing plastic samples lead to a strongdiscoloration within a very short time when exposed to weathering.Plastic samples containing the present combination of components a) andb) exhibit only minimal color changes.

[0036] Triclosan containing plastic samples exhibit a reduced lightstability. Plastic samples containing the present combination ofcomponents a) and b) exhibit physical properties that are comparable toa control formulation without antimicrobial agents.

[0037] The plastic films, fibers and articles of the present inventionare advantageously employed for applications that require long-termhygienic activity on the surface, e.g., medical devices, hand rails,door handles, etc. The antimicrobial plastic films, fibers and articlesof the present invention are used for example in hospitals, households,public institutions, ventilation systems, air cleaning and airconditioning systems and waste disposal systems. Plastic articlesexposed to outdoor weathering that may have incorporated therein theantimicrobial mixture of the present invention are for example wastecontainers, swimming pool equipment, outdoor swing set equipment, slidesand the like, and stadium seats.

[0038] The plastic films, fibers and articles of the present inventionexhibit high antimicrobial activity at the surface. The antimicrobialactivity remains after repeated washings.

[0039] The plastic films, fibers and articles of the present invention,that is to say, the plastic materials, may also have incorporatedtherein one or more of the following known additives:

[0040] 1. Antioxidants

[0041] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

[0042] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

[0043] 1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0044] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

[0045] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

[0046] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methly-6-cyclohexylphenol,)2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0047] 1.7. Benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt.

[0048] 1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0049] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0050] 1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis-(3,5-di-tert-butyl-4-hydroxyanilino-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0051] 1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0052] 1.12. Acylaminophenols, for example 4-hydroxy-lauric acidanilide, 4-hydroxy-stearic acid anilide,2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine andoctyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

[0053] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0054] 1.14. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0055] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0056] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0057] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

[0058] 1.18. Ascorbic acid (vitamin C)

[0059] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono-and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

[0060] 2. UV Absorbers and Light Stabilizers

[0061] 2.1.2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example knowncommercial hydroxyphenyl-2H-benzotriazoles and benzotriazoles asdisclosed in, U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910;3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004;4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905,4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071;5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987 and5,977,219, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5trifluoromethyl-2H-benzotriazol-2-yl)-5-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

[0062] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0063] 2.3. Esters of substituted and unsubstituted benzoic acids, asfor example 4-tertbutyl-phenyl salicylate, phenyl salicylate,octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0064] 2.4. Acrylates and malonates, for example,α-cyano-β,β-diphenylacrylic acid ethyl ester or isooctyl ester,α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvor® PR25,dimethyl p-methoxybenzylidenemalonate (CAS# 7443-25-6), and Sanduvor®PR31, di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate (CAS#147783-69-5).

[0065] 2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0066] 2.6. Sterically hindered amine stabilizers, for example4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, linear orcyclic condensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-amino-propylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy-and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

[0067] The sterically hindered amine may also be one of the compoundsdescribed in GB-A-2301106 as component I-a), I-b), I-c), I-d), I-e),I-f), I-g), I-h), I-i), I-j), I-k) or I-l), in particular the lightstabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2, 1-d-1, 1-d-2, 1-d-3,1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed on pages 68 to 73 of saidGB-A-2301106.

[0068] The sterically hindered amine may also be one of the compoundsdescribed in EP 782994, for example compounds as described in claims 10or 38 or in Examples 1-12 or D-1 to D-5 therein.

[0069] 2.7. Sterically hindered amines substituted on the N-atom by ahydroxy-substituted alkoxy group, for example compounds such as1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidinewith a carbon radical from t-amylalcohol,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate and2,4-bis{(N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine.

[0070] 2.8. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0071] 2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example knowncommercial tris-aryl-o-hydroxyphenyl-s-triazines and triazines asdisclosed in, WO 96/28431, EP 434608, EP 941989, GB 2,317,893, U.S. Pat.Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067;5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518;5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,942,626; 5,959,008;5,998,116 and 6,013,704, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,Cyasorb® 1164, Cytec Corp,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxy-propyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(*denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)-phenyl]s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-hydroxyphenyl)-s-triazine.

[0072] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0073] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

[0074] Especially preferred are the following phosphites:

[0075] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, CibaSpecialty Chemicals Corp.), tris(nonylphenyl) phosphate,

[0076] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0077] 6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-hep-tadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydro-xylamine derived from hydrogenated tallow amine.

[0078] 7. Amine oxides, for example amine oxide derivatives as disclosedin U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

[0079] 8. Benzofuranones and indolinones, for example those disclosed inU.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, Irganox®HP-136, Ciba Specialty Chemicals Corp., and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0080] 9. Thiosynergists, for example dilauryl thiodipropionate ordistearyl thiodipropionate.

[0081] 10. Peroxide scavengers, for example esters of β-thiodipropionicacid, for example the lauryl, stearyl, myristyl, or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

[0082] 11. Polyamide stabilizers, for example copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

[0083] 12. Basic co-stabilizers, for example melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acids,for example, calcium stearate rate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

[0084]13. Nucleating agents, for example inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds such as ionic copolymers (ionomers).

[0085] 14. Fillers and reinforcing agents, for example calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0086] 15. Other additives, for example plasticizers, lubricants,emulsifiers, pigments, dyes, optical brighteners, rheology additives,catalysts, flow-control agents, slip agents, crosslinking agents,crosslinking boosters, halogen scavengers, smoke inhibitors,flameproofing agents, antistatic agents, clarifiers such as substitutedand unsubstituted bisbenzylidene sorbitols, benzoxazinone UV absorberssuch as 2,2′-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS#18600-59-4), and blowing agents.

[0087] 16. Other biocides, for example fungicides such as3,5-dimethyl-tetrahydro-1,3,5-2H-thiodiazin-2-thione,Bis-tributyltinoxide, 4.5-dichlor-2-n-octyl-4-isothiazolin-3-one,N-butyl-benzisothiazoline, 10.10′-oxybisphenoxyarsine,zinc-2-pyridinthiol-1-oxide, etc., and algicides such as2-methylthio-4-cyclopropylamino-6-(α,β-dimethylpropylamino)-s-triazine,2-methylthio-4-cyclopropylamino-6-tert-butylamino-s-triazine,2-methylthio-4-ethylamino-6-(α,β-dimethylpropylamino)-s-triazine, etc.

[0088] In general the plastic resins with antimicrobial activityaccording to the present invention may be selected from:

[0089] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE) and medium densitypolyethylene (MDPE).

[0090] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0091] a) radical polymerization (normally under high pressure and atelevated temperature).

[0092] b) catalytic polymerization using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerization medium. The catalysts can be used by themselves inthe polymerization or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0093] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPF) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0094] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0095] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0096] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0097] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene, styrene/unsaturatedester, styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0098] 7. Graft copolymers of styrene or a-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, SAN, MBS, ASA or AES polymers.

[0099] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

[0100] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0101] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

[0102] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0103] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bis-glycidyl ethers.

[0104] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0105] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0106] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0107] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0108] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0109] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polytrimethylene terephthalate, polybutyleneterephthalate, poly-1,4-dimethylolcyclohexane terephthalate andpolyhydroxybenzoates, as well as block copolyether esters derived fromhydroxyl-terminated polyethers; and also polyesters modified withpolycarbonates or MBS. Polyesters and polyester copolymers as defined inU.S. Pat. No. 5,807,932 (column 2, line 53), incorporated herein byreference.

[0110] 19. Polycarbonates and polyester carbonates.

[0111] 20. Polysulfones, polyether sulfones and polyether ketones.

[0112] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0113] 22. Drying and non-drying alkyd resins.

[0114] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0115] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0116] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0117] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bis glycidyl ethers or from cycloaliphatic diepoxides.

[0118] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0119] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/-EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

[0120] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oils and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0121] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0122] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0123] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0124] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0125] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0126] Preferably, the plastic resin is selected from the groupconsisting of LDPE, HDPE, MDPE, PP, ABS, SAN, PS, PMMA, PET, polyamide,PVC, polymer latex, PUR, TPU, UF and UP.

[0127] The mixture of components a) and b) is preferably present in theantimicrobial plastic film, fiber or article in an amount of about 0.005to about 10% by weight, relative to the plastic material. An amount offrom about 0.01 to about 5% by weight or about 0.05 to about 3% byweight of the mixture of components a) and b) relative to the plasticmaterial is especially preferred

[0128] The mixture of components a) and b) and optional furtheradditives may be added to the plastic resin, e.g. the polyolefin,individually or mixed with one another. If desired, the individualcomponents of an additive mixture can be mixed with one another in themelt (melt blending) before incorporation into the plastic material.

[0129] The incorporation of the mixture of components a) and b) andoptional further additives into the plastic material is carried out byknown methods such as dry mixing in the form of a powder, or wet mixingin the form of solutions or suspensions. Components a) and b) andoptional further additives may be incorporated, for example, before orafter molding or also by applying the dissolved or dispersed stabilizermixture to the plastic material, with or without subsequent evaporationof the solvent. The mixture of components a) and b) and optional furtheradditives can also be added to the plastic material in the form of amasterbatch which contains these components in a concentration of, forexample, about 2.5% to about 70% by weight; in such operations, thepolymer can be used in the form of powder, granules, solutions,suspensions or in the form of latices.

[0130] If added to a plastic resin in the form of a masterbatch orconcentrate, the novel antimicrobial mixture of components a) and b) isadded via carriers such as LDPE, HDPE, MDPE, PP, ABS, SAN, PS,acrylates, PMMA, polyamide, polyesters, PVC, polymer latex, styrene,polyol, TPU, unsaturated esters, urea, paraformaldehyde, water emulsion,etc. The total concentration of a)+b) in the carriers is from about 2.5%to about 70% by weight based on the weight of the carrier.

[0131] Components a) and b) and optional further additives can also beadded before, during or after polymerization or crosslinking.

[0132] Components a) and b) and optional further additives can beincorporated into the plastic material in pure form or encapsulated inwaxes, oils or polymers.

[0133] Components a) and b) and optional further additives can also besprayed onto the plastic material. They are able to dilute otheradditives (for example the conventional additives indicated above) ormonomers or their melts so that they can be sprayed also together withthese additives onto the plastic material. Addition by spraying duringthe deactivation of the polymerization catalysts is particularlyadvantageous, it being possible to carry out spraying using, forexample, the steam used for deactivation.

[0134] In the case of spherically polymerized polyolefins it may, forexample, be advantageous to apply components a) and b) and optionallytogether with other additives, by spraying.

[0135] The following examples illustrate the invention in more detail.They are not to be construed as limiting the instant invention in anymanner whatsoever. The invention is declared to cover all changes andmodifications of the specific examples which do not constitute departurefrom the spirit and scope of the invention. Parts and percentages are byweight.

EXAMPLE 1

[0136] High density polyethylene, Borealis MS 6591, is dry blended withthe antimicrobial agents set forth in Table 1. The levels are percent byweight based on the HDPE. The mixtures are compounded with a twin screwat a maximum temperature of 220° C. The samples are injection moldedinto 2 mm plaques at a maximum temperature of 220° C. The plaques aresubjected to accelerated weathering in a Ci65 Xenon Arc Weather-Ometerat 63° C., 0.35 W/m² with a spray cycle. Yellowness Index results arefound in Table 1. TABLE I Antimicrobial Agents 0 h 24 h 48 h 96 h 500 hnone 1.9  2.7  1.9  0.3 −0.8 0.2% Irgaguard ® B1000 4.0 57.1 60.8 62.566.9 0.2% Irgaguard ® B1000 + 1.1 38.9 42.5 45.4 49.9 0.1% BM-102GA 1.10.5% Irgaguard ® B1000 + 2.2 21.2 27.9 33.1 33.4 0.1% BM-102GA

[0137] It can be seen that the formulations of the present invention,using a combination of antimicrobial agents of components a) and b),provide superior resistance to yellowing upon accelerated weathering.

EXAMPLE 2

[0138] Polypropylene homopolymer, Montell Pro-fax 6301, is dry blendedwith the antimicrobial agents set forth in Table 2. The levels arepercent by weight based on the polypropylene. The mixtures areadditionally formulated with 0.06% Irgastab® FS-301, 0.06% Tinuvin® 783and 0.05% calcium stearate. The polypropylene samples are spun intofibers at 260° C. The fibers are subjected to accelerated weathering ina Ci65 Xenon Arc Weather-Ometer at 63° C., 0.35 W/m² with a spray cycle.Yellowness Index results are found in Table 2. TABLE 2 AntimicrobialAgents 0 h 12 h 68 h 157 h 392 h none 1.7 1.8 1.5 1.1 1.4 0.5%Irgaguard ® B1000 2.0 24.1 16.9 9.5 failure 0.25% Irgaguard ® B1000 +1.9 9.3 7.3 4.9 2.8 0.25% BM-102GA

[0139] It can be seen that the formulations of the present invention,using a combination of antimicrobial agents of components a) and b),provide superior resistance to yellowing upon accelerated weathering.

[0140] Irgaguard® B1000 is 2,4,4′-trichloro-2′-hydroxydiphenyl ether,Ciba Specialty Chemicals. BM-102GA (Kanebo) is a surface-modifiedsilver-containing zeolite.

[0141] Tinuvin®783 is a combination of sterically hindered amine lightstabilizers available from Ciba Specialty Chemicals, Tinuvin®622 andChimassorbe®944:

[0142] Irgastab® FS-301, Ciba Specialty Chemicals, is a combination ofIrgafos® 168 and Irgastab® FS-042. Irgafos® 168 istris-(2,4-di-tert-butylphenyl)phosphite. Irgastab® FS-042 is theN,N-di(alkyl)hydroxylamine produced by the direct oxidation ofN,N-di(hydrogenated tallow)amine.

What is claimed is:
 1. A mixture of antimicrobial agents for plasticsapplications which comprises a) at least one phenolic antimicrobialcompound, and b) at least one inorganic antimicrobial compound, whereinthe phenolic antimicrobial compound is of the formula (I)

wherein n is 0or 1, R₁ and R₂ are hydrogen or chlorine, R₃ is hydrogenor hydroxyl, R₄, R₅ and R₆ are hydrogen or chlorine, R₇ is hydroxyl, andX is —O— or —CH₂-, and wherein the inorganic antimicrobial compound isselected from the group consisting of zinc oxide, copper and coppercompounds, silver, colloidal silver, silver nitrate, silver sulphate,silver chloride, silver complexes, metal-containing zeolites andsurface-modified metal-containing zeolites, wherein the ratio ofcomponents a):b) is from about 1:9 to about 9:1.
 2. A mixture ofantimicrobial agents according to claim 1 wherein the phenolicantimicrobial compound is selected from the group consisting ofo-benzyl-phenol, 2-benzyl-4-chloro-phenol,2,4,4′-trichloro-2′-hydroxydiphenyl ether,4,4′-dichloro-2-hydroxydiphenyl ether,5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol,2,2′-methylenbis-(4-chloro-phenol) and 2,4,6-trichlorophenol.
 3. Amixture of antimicrobial agents according to claim 2 wherein thephenolic antimicrobial compound is selected from the group consisting of2,4,4′-trichloro-2′-hydroxydiphenyl ether and4,4′-dichloro-2-hydroxydiphenyl ether.
 4. A mixture of antimicrobialagents according to claim 1 wherein the inorganic antimicrobial agent isa metal-containing zeolite or a surface-modified metal-containingzeolite.
 5. A mixture of antimicrobial agents according to claim 4wherein the metal is selected from the group consisting of silver,copper, zinc, zirconium and combinations thereof.
 6. A mixture ofantimicrobial agents according to claim 5 wherein the metal is selectedfrom the group consisting of silver and combinations of silver withcopper, zinc or zirconium.
 7. A mixture of antimicrobial agentsaccording to claim 4 wherein the inorganic antimicrobial agent is ametal-containing surface-modified zeolite wherein the metal is selectedfrom the group consisting of silver and combinations of silver withcopper, zinc or zirconium.
 8. A mixture of antimicrobial agentsaccording to claim 7 wherein component a) is2,4,4′-trichloro-2′-hydroxydiphenyl ether and wherein component b) is asurface-modified metal-containing zeolite.
 9. An antimicrobial plasticfilm, fiber or article which has incorporated therein a mixture ofantimicrobial agents according to claim
 1. 10. An antimicrobial plasticfilm, fiber or article according to claim 9 in which the plastic isselected from the group consisting of polyethylene, polypropylene,acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrilecopolymer (SAN), polystyrene (PS), polymethyl methacrylate (PMMA),polyester, polyamide, polyvinyl chloride (PVC), polymer latex,polyurethane (PUR), thermoplastic urethane (TPU), urea formaldehyderesin (UF) and unsaturated polyester (UP).
 11. An antimicrobial plasticfilm, fiber or article according to claim 10 in which the plastic isselected from low-density polyethylene (LDPE), high-density polyethylene(HDPE), polypropylene (PP), polyester and polyamide.
 12. Anantimicrobial plastic film, fiber or article according to claim 9 inwhich the mixture of components a) and b) is present from about 0.005 toabout 10% by weight based on the plastic film, fiber or article.
 13. Anantimicrobial plastic film, fiber or article according to claim 12 inwhich the mixture of components a) and b) is present from about 0.01 toabout 5% by weight based on the plastic film, fiber or article.
 14. Anantimicrobial plastic film, fiber or article according to claim 13 inwhich the mixture of components a) and b) is present from about 0.05 toabout 3% by weight based on the plastic film, fiber or article.
 15. Anantimicrobial plastic film, fiber or article according to claim 9 whichadditionally comprises at least one co-additive selected from the groupconsisting of antioxidants, ultraviolet light absorbers, hinderedamines, phosphites or phosphonites, hydroxylamines, nitrones,benzofuran-2-ones, thiosynergists, polyamide stabilizers, metalstearates, nucleating agents, fillers, reinforcing agents, lubricants,emulsifiers, dyes, pigments, optical brighteners, flame retardants,antistatic agents and blowing agents.
 16. A masterbatch or concentrateof a mixture of antimicrobial agents according to claim 1 wherein thecomponents a) and b) are present at a total concentration of about 2.5%to about 70% by weight based on the weight of the carrier, and whereinthe carrier is selected from the group consisting of polyethylene,polypropylene (PP), acrylonitrile-butadiene-styrene terpolymer (ABS),styrene-acrylonitrile copolymer (SAN), polystyrene (PS), acrylates,polymethyl methacrylate (PMMA), polyamide, polyesters, polyvinylchloride (PVC), polymer latex, styrene, polyol, thermoplastic urethane(TPU), unsaturated esters, urea, paraformaldehyde and water emulsion.